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| United States Patent |
5,304,596
|
|
Moriya
, et al.
|
April 19, 1994
|
Polyolefin resin compositions containing a cycloolefin resin and
processes for the preparation thereof
Abstract
Polyolefin resin compositions having a sea and island structure wherein
cycloolefin resin, graft modified cycloolefin resin and graft modified
elastomer components are finely dispersed in polyamide by melt kneading
the cycloolefin resin, graft modified cycloolefin resin, graft modified
elastomer and polyamide. Molded products formed by using the polyolefin
resin compositions of the present invention are high in impact strength
and surface characteristics, particularly less in surface delamination,
and also excellent in surface glossiness. The molded products are low in
water absorption properties and also excellent in oil resistance.
| Inventors:
|
Moriya; Satoru (Kuga, JP);
Ishimoto; Akio (Kuga, JP);
Takahashi; Mamoru (Kuga, JP)
|
| Assignee:
|
Mitsui Petrochemical Industries, Ltd. (Tokyo, JP)
|
| Appl. No.:
|
704888 |
| Filed:
|
May 23, 1991 |
Foreign Application Priority Data
| Current U.S. Class: |
525/66 |
| Intern'l Class: |
C08L 023/08; C08L 045/00 |
| Field of Search: |
525/66
|
References Cited
U.S. Patent Documents
| 3554886 | Jan., 1971 | Colomb, Jr. et al. | 525/66.
|
| 4174358 | Nov., 1979 | Epstein.
| |
| 4918133 | Apr., 1990 | Moriya et al. | 524/518.
|
Other References
DATA BASE WPIL, accession No. 86-094470 [15], Derwent Publications Ltd,
London, GB; & DD-A-230 828 (VEB LEUNA-WERK) (1986).
DATA BASE WPIL, accession No. 85-196942 [33], Derwent Publications Ltd,
London, GB; & DD-A-203 059 (VEB LEUNA-WERK) (1985).
DATA BASE WPIL, accession No. 86-096681 [15], Derwent Publications Ltd,
London, GB; & JP-A-61 040 356 (DAINIPPON INK.) (1986).
|
Primary Examiner: Kight, III; John
Assistant Examiner: Mullis; Jeffrey Culpeper
Attorney, Agent or Firm: Sherman and Shalloway
Claims
What is claimed is:
1. A polyolefin resin composition containing
(a) at least one cycloolefin resin selected from the group consisting of
(a-1) a copolymer of ethylene and cycloolefin represented by the following
formula (I),
(a-2) a ring opening homopolymer of cycloolefin represented by the
following formula (I),
(a-3) a ring opening copolymer of at least two different cycloolefins
represented by the following formula (I), and
(a-4) a hydrogenation product of the above-mentioned (a-2) or (a3),
(b) a graft modification product of the above-mentioned (a-1), (a-2), (a-3)
or (a-4) with an unsaturated carboxylic acid or a derivative thereof,
(c) an .alpha.-olefin copolymer graft modified with an unsaturated
carboxylic acid or a derivative thereof and having a tensile modulus at
23.degree. C. of 0.1-2000 kg/cm.sup.2, and
(d) polyamide, said components (a), (b), (c) and (d) amounting, based on
100 parts by weight of the composition, to 0-59.5 parts by weight, 0.5-60
parts by weight, 2-30 parts by weight and 20-60 parts by weight,
respectively;
##STR23##
wherein n is 0 or 1, m is 0 to 3, q is 0 or 1, R.sup.1 to R.sup.18,
R.sup.a and R.sup.b independently represent an atom or a group selected
from the group consisting of hydrogen atom, halogen atom and hydrocarbon
group, wherein the hydrocarbon group is selected from the group consisting
of alkyl containing 1 to 6 carbon atoms and cycloalkyl containing 3 to 6
carbon atoms, R.sup.15 to R.sup.18 may be bonded together to form a
monocyclic group or a polycyclic group which optionally has one or more
double bonds.
2. The polyolefin resin composition as claimed in claim 1 wherein the
polyolefin resin composition is a resin composition formed from the
cycloolefin resin (a) which is the copolymer (a-1) of ethylene and
cycloolefin of the above-mentioned formula (I) and the graft modification
product (b) which is the graft modified of said copolymer (a-1), the graft
modified .alpha.-olefin copolymer (c) and the polyamide (d) totaling to
100 parts by weight, said components (a-1), (b), (c) and (d) amounting to
greater than 0 up to 59.5 parts by weight, 0.5-60 parts by weight, 2-30
parts by weight and 20-60 parts by weight, respectively.
3. The polyolefin resin composition as claimed in claim 1 or 2 wherein the
component (a-1) has a softening temperature of 70.degree.-250.degree. C.
and an intrinsic viscosity [.eta.], as measured in decalin at 130.degree.
C., of 0.3-2.0 dl/g.
4. The polyolefin resin composition as claimed in claim 1 or 2 wherein the
component (b) has a softening temperature of 0.degree.-250.degree. C. and
an intrinsic viscosity [.eta.], as measured in decalin at 130.degree. C.,
of 0.1-2.0 dl/g.
5. The polyolefin resin composition as claimed in claim 1 or 2 wherein the
graft modified .alpha.-olefin copolymer (c) is a graft modification
product of an amorphous or low crystalline elastomeric .alpha.-olefin
copolymer formed from two kinds of .alpha.-olefins.
6. The polyolefin resin composition as claimed in claim 1 or 2 wherein the
graft modification product (b) of the component (a-1), (a-2), (a-3) or
(a-4) is a product graft modified with maleic anhydride.
7. The polyolefin resin composition as claimed in claim 1 or 2 wherein the
graft modified .alpha.-olefin copolymer (c) is a product graft modified
with maleic anhydride.
8. A process for the preparation of a polyolefin resin composition which
comprises melt kneading
(a) at least one cycloolefin resin selected from the group consisting of
(a-1) a copolymer of ethylene and cycloolefin represented by the following
formula (I),
(a-2) a ring opening homopolymer of cycloolefin represented by the
following formula (I),
(a-3) a ring opening copolymer of at least two different cycloolefins
represented by the following formula (I), and
(a-4) a hydrogenation product of the above-mentioned (a-2) or (a-3)
(b) a graft modification product of the above-mentioned (a-1), (a-2), (a-3)
or (a-4) with an unsaturated carboxylic acid or a derivative thereof,
(c) an .alpha.-olefin copolymer graft modified with an unsaturated
carboxylic acid or a derivative thereof and having a tensile modulus at
23.degree. C. of 0.1-2000 kg/cm.sup.2, and
(d) polyamide all together;
##STR24##
wherein n is 0 or 1, m is 0 to 3, q is 0 or 1, R.sup.1 to R.sup.18,
R.sup.a and R.sup.b independently represent an atom or a group selected
from the group consisting of hydrogen atom, halogen atom and hydrocarbon
group, wherein the hydrocarbon group is selected from the group consisting
of alkyl containing 1 to 6 carbon atoms and cycloalkyl containing 3 to 6
carbon atoms, R.sup.15 to R.sup.18 may be bonded together to form a
monocyclic group or a polycyclic group which optionally has one or more
double bonds.
9. A process for the preparation of a polyolefin resin composition which
comprises melt kneading
(a) at least one cycloolefin resin selected from the group consisting of
(a-1) a copolymer of ethylene and cycloolefin represented by the following
formula (I),
(a-2) a ring opening homopolymer of cycloolefin represented by the
following formula (I),
(a-3) a ring opening copolymer of at least two different cycloolefins
represented by the following formula (I), and
(a-4) a hydrogenation product of the above-mentioned (a-2) or (a-3),
(b) a graft modification product of the above-mentioned (a-1), (a-2), (a-3)
or (a-4) with an unsaturated carboxylic acid or a derivative thereof, and
(c) an .alpha.-olefin copolymer graft modified with an unsaturated
carboxylic acid or a derivative thereof and having a tensile modulus at
23.degree. C. of 0.1-2000 kg/cm.sup.2, and adding
(d) polyamide to the kneaded product obtained in a molten state, followed
by kneading the resulting mixture;
##STR25##
wherein n is 0 or 1, m is 0 to 3, q is 0 or 1, R.sup.1 to R.sup.18,
R.sup.a and R.sup.b independently represent an atom or a group selected
from the group consisting of hydrogen atom, halogen atom and hydrocarbon
group, wherein the hydrocarbon group is selected from the group consisting
of alkyl containing 1 to 6 carbon atoms and cycloalkyl containing 3 to 6
carbon atoms, R.sup.15 to R.sup.18 may be bonded together to form a
monocyclic group or a polycyclic group which optionally has one or more
double bonds.
10. The process for the preparation of a polyolefin resin composition as
claimed in claim 9 wherein the polyamide (d) is added in a solid state to
the molten resin stream of the components (a), (b) and (c).
11. A polyolefin resin composition containing
(a) at least one cycloolefin resin selected from the group consisting of
(a-1) a copolymer of ethylene and cycloolefin represented by the following
formula (I),
(a-2) a ring opening homopolymer of cycloolefin represented by the
following formula (I),
(a-3) a ring opening copolymer comprising two different cycloolefins
represented by the following formula (I), and
(a-4) a hydrogenation product of the above-mentioned (a-2) or (a-3)
(b) a graft modification product of the above-mentioned (a-1), (a-2), (a-3)
or (a-4) with an unsaturated carboxylic acid or a derivative thereof, and
(c) an .alpha.-olefin copolymer graft modified with an unsaturated
carboxylic acid or a derivative thereof and having a tensile modulus at
23.degree. C. of 0.1-2000 kg/cm.sup.2, and
(d) polyamide, said components (a), (b), (c) and (d) amounting, based on
100 parts by weight of the composition, to 0 to 40 parts by weight, 0.5-55
parts by weight, 5-30 parts by weight and 25-60 parts by weight,
respectively;
##STR26##
wherein n is 0 or 1, m is 0 to 3, q is 0 or 1, R.sup.1 to R.sup.18,
R.sup.a and R.sup.b independently represent an atom or a group selected
from the group consisting of hydrogen atom, halogen atom and hydrocarbon
group, wherein the hydrocarbon group is selected from the group consisting
of alkyl containing 1 to 6 carbon atoms and cycloalkyl containing 3 to 6
carbon atoms, R.sup.15 to R.sup.18 may be bonded together to form a
monocyclic group or a polycyclic group which optionally has one or more
double bonds.
12. The polyolefin resin composition as claimed in claim 11 wherein the
polyolefin resin composition is a resin composition formed from the
cycloolefin resin (a) which is the copolymer (a-1) of ethylene and
cycloolefin of the above-mentioned formula (I) and the graft modification
product (b) which is the graft modified of said copolymer (a-1), the graft
modified .alpha.-olefin copolymer (c) and the polyamide (d) totaling to
100 parts by weight, said components (a-1), (b), (c) and (d) amounting to
greater than 0 up to 40 parts by weight, 0.5-55 parts by weight, 5-30
parts by weight and 30-55 parts by weight, respectively.
13. The polyolefin resin composition as claimed in claim 11 wherein the
polyolefin resin composition is a resin composition formed from the
cycloolefin resin (a) which is the ring opening homopolymer (a-2) of
cycloolefin of the above-mentioned formula (I) and the graft modification
product (b) which is the graft modified of said homopolymer (a-2), the
graft modified .alpha.-olefin copolymer (c) and the polyamide (d) totaling
to 100 parts by weight, said components (a-2), (b), (c) and (d) amounting
to greater than 0 up to 40 parts by weight, 0.5-55 parts by weight, 5-30
parts by weight and 30-55 parts by weight, respectively.
14. The polyolefin resin composition as claimed in claim 11 wherein the
polyolefin resin composition is a resin composition formed from the
cycloolefin resin (a) which is the ring opening copolymer (a-3) comprising
two different cycloolefins of the above-mentioned formula (I) and the
graft modification product (b) which is the graft modified of said
copolymer (a-3), the graft modified .alpha.-olefin copolymer and the
polyamide (d) totaling to 100 parts by weight, said components (a-3), (b),
(c) and (d) amounting to greater than 0 up to 40 parts by weight, 0.5-55
parts by weight, 5-30 parts by weight and 30-55 parts by weight,
respectively.
15. The polyolefin resin composition as claimed in claim 11, 12, 13 or 14
wherein the graft modification .alpha.-olefin copolymer (c) is a graft
modification product of an amorphous or low crystalline elastomeric
.alpha.-olefin copolymer comprising two different .alpha.-olefins.
16. The polyolefin resin composition as claimed in claim 11, 12, 13 or 14
wherein the graft modification product (b) of the component (a-1), (a-2),
(a-3) or (a-4) is a product graft modified with maleic anhydride.
17. The polyolefin resin composition of claim 1 or 11 wherein in the
formula (I) n=1.
18. The polyolefin resin composition of claim 1 or 11 wherein in the
formula (I) m=1 to 3.
19. The process of claim 8 or 9 for the preparation of a polyolefin resin
wherein in the formula (I) n=1.
20. The process of claim 8 or 9 for the preparation of a polyolefin resin
wherein in the formula (I) m=1 to 3.
Description
FIELD OF THE INVENTION
This invention relates to polyolefin resin compositions containing a
cycloolefin resin, a graft modified cycloolefin resin, a graft modified
elastomer and polyamide and having excellent impact resistance, and to
processes for the preparation thereof.
BACKGROUND OF THE INVENTION
Conventionally, polyolefins are known as resins excellent in chemical
resistance and solvent resistance. However, when polyolefin is low in
crystallinity index, it cannot be said that the polyolefin has sufficient
rigidity, heat resistance and solvent resistance.
On that account, there is adopted a process for improving polyolefin in
heat resistance and rigidity by the addition thereto of a nucleating agent
or a process for enhancing polyolefin in crystallinity index by cooling a
molten polyolefin gradually. However, it is hard to say that the effect
obtained thereby is sufficient.
Apart from such polyolefins as referred to above, it is reported that
copolymers obtained by the reaction of ethylene with bulky monomers are
excellent in properties such as heat resistance in comparison with
conventionally known polyolefins (see, for example, U.S. Pat. No.
2,883,372 and Japanese Patent Publication No. 14910/1971).
In this connection, on the basis of the acquired information on the fact
that cyclic random copolymers obtained by copolymerization of specific
cycloolefins as bulky monomers and ethylene are excellent in heat
resistance, heat aging characteristics, dielectric characteristics and
rigidity, the present applicant has already proposed random copolymers
obtained by using specific cycloolefins (see Japanese Patent L-O-P
Publications Nos. 168708/1985, 120816/1986, 115912/1986, 115916/1986,
271308/1986, 272216/1986, 252406/1987 and 252407/1987).
On the other hand, an attempt has been made to incorporate other resins
into polyamides for the purpose of improving characteristics inherent in
polyamides. In spite of various improvements suggested as above, there was
much room for further improvement on various characteristics such as water
absorption properties, molding shrinkage or heat-resisting rigidity.
OBJECT OF THE INVENTION
The present invention intends to provide, as its object, compositions
containing the above-mentioned cycloolefin resin and capable of forming
molded articles excellent particularly in mechanical characteristics such
as impact strength, and physical properties such as glossiness, solvent
resistance and low water absorption properties, and processes for the
preparation of said compositions.
More particularly, the object of the invention is to provide, without
sacrifice of excellent characteristics of cycloolefin resin, cycloolefin
random copolymer-containing resin compositions capable of forming molded
articles excellent particularly in mechanical characteristics such as
impact resistance, etc., solvent resistance and surface glossiness, and
also low in water absorption, and processes for the preparation of said
resin compositions.
SUMMARY OF THE INVENTION
The polyolefin resin composition of the present invention is characterized
by containing,
(a) at least one cycloolefin resin selected from the group consisting of
(a-1) a copolymer of ethylene and cycloolefin represented by the following
formula [I],
(a-2) a ring opening homopolymer of cycloolefin represented by the
following formula [I],
(a-3) a ring opening copolymer of at least two kinds of cycloolefins
represented by the following formula [I], and
(a-4) a hydrogenation product of the above-mentioned (a-2) or (a-3),
(b) a graft modification product of the above-mentioned (a-1), (a-2), (a-3)
or (a-4),
(c) an elastomer graft modified with an unsaturated carboxylic acid or a
derivative thereof and having a tensile modulus at 23.degree. C. of
0.1-2000 kg/cm.sup.2, and
(d) polyamide, said components (a), (b), (c) and (d) amounting, based on
100 parts by weight of the composition, to 0-59.5 parts by weight, 0.5-60
parts by weight, 2-30 parts by weight and 20-60 parts by weight,
respectively;
##STR1##
wherein n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R.sup.1
to R.sup.18, R.sup.a and R.sup.b independently represent an atom or a
group selected from the group consisting of hydrogen atom, halogen atom
and hydrocarbon group, R.sup.15 to R.sup.18 may be bonded together to form
a monocyclic group or a polycyclic group which may have double bond(s),
and R.sup.15 and R.sup.16, or R.sup.17 and R.sup.18 may form an alkylidene
group.
The process for the preparation of the polyolefin resin composition of the
invention is characterized by melt kneading
(a) at least one cycloolefin resin selected from the group consisting of
(a-1) a copolymer of ethylene and cycloolefin represented by the
above-mentioned formula [I],
(a-2) a ring opening homopolymer of cycloolefin represented by the
above-mentioned formula [I],
(a-3) a ring opening copolymer of at least two kinds of cycloolefins
represented by the above-mentioned formula [I], and
(a-4) a hydrogenation product of the above-mentioned (a-2) or (a-3),
(b) a graft modification product of the above-mentioned (a-1), (a-2), (a-3)
or (a-4),
(c) an elastomer graft modified with an unsaturated carboxylic acid or a
derivative thereof and having a tensile modulus at 23.degree. C. of
0.1-2000 kg/cm.sup.2, and
(d) polyamide together.
In the process for the preparation of the polyolefin resin composition of
the invention, it is particularly desirable that the cycloolefin resin
(a), the graft modification product (b) of the cycloolefin resin (a) and
the graft modified elastomer (c) are first melt kneaded together to give a
kneaded product, and the polyamide (d) is then added to the kneaded
product in a molten state, followed by kneading.
DETAILED DESCRIPTION OF THE INVENTION
The polyolefin resin composition of the present invention contains (a) a
cycloolefin resin, (b) a graft modification product of the cycloolefin
resin, (c) elastomer graft modified with an unsaturated carboxylic acid
and a derivative thereof and having a tensile modulus at 23.degree. C. of
0.1-2000 kg/cm.sup.2, and (d) polyamide, the amount, based on 100 parts by
weight of the composition containing the components (a), (b), (c) and (d),
of said component (a) being 0-59.5 parts by weight, preferably 0-40 parts
by weight and especially 0-35 parts by weight, of said component (b) being
0.5-60 parts by weight, preferably 0.5-55 parts by weight and especially
5-55 parts by weight, of said component (c) being 2-30 parts by weight,
preferably 5-30 parts by weight and especially 5-25 parts by weight, and
of said component (d) being 20-60 parts by weight, preferably 25-60 parts
by weight and especially 30-55 parts by weight.
In the polyolefin resin composition of the invention, a so-called "sea and
island structure" is formed. In this case, it is considered that the resin
composition comes to have morphologically a so-called "sea moiety" formed
by the polyamide and a so-called "island moiety" formed by the components
(a), (b) and (c).
Molded products that can be obtained by using this resin composition are
high in impact strength, excellent in surface profile, particularly less
in delamination and in surface glossiness. The molded articles thus
obtained are low in water absorption properties and also excellent in oil
resistance.
As the component (a), that is, the cycloolefin resin, used in the process
for the preparation of the polyolefin resin composition of the invention,
there may be mentioned
(a-1) a copolymer of ethylene and cycloolefin represented by the following
formula [I],
(a-2) a ring opening homopolymer of cycloolefin represented by the
following formula [I],
(a-3) a ring opening copolymer of at least two kinds of cycloolefins
represented by the following formula [I], and
(a-4) a hydrogenation product of the above-mentioned (a-2) or (a-3).
These cycloolefin resins as illustrated above may be used either singly or
in combination with other different polymer or copolymer.
##STR2##
In the above-mentioned formula [I], n is 0 (zero) or 1, preferably 0
(zero), m is 0 (zero) or a positive integer, preferably 0-3, and q is 0 or
1.
R.sup.1 -R.sup.18, R.sup.a and R.sup.b (formula [I]) individually represent
an atom or group selected from the group consisting of hydrogen, halogen
and hydrocarbon, wherein the halogen includes, for example, fluorine,
chlorine, bromine and iodine atoms, and the hydrocarbon group includes
usually alkyl of 1-6 carbon atoms and cycloalkyl of 3-6 carbon atoms.
Concrete examples of the alkyl include methyl, ethyl, isopropyl, isobutyl
and amyl, and those of the cycloalkyl include cyclohexyl, cyclopropyl,
cyclobutyl and cyclopentyl.
In the above formula [I], when "q" is 0 (zero), the ring represented by
using "q" forms five-member ring.
In the above mentioned formula [I], R.sup.15 -R.sup.18 may form, linking
together (in combination), a mono- or polycyclic ring which may have
double bond. The mono- or polycyclic rings are described below. Further,
these rings may have substituting groups such as a methyl group.
##STR3##
The carbon atoms indicated by 1 and 2 in the above-exemplified formulas
represent carbon atoms of an alicyclic structure in the formula [I],
wherein groups designated by R.sup.15 to R.sup.18 are bonded to the carbon
atoms. And R.sup.15 together with R.sup.16, or R.sup.17 together with
R.sup.18 may form an alkylidene of 2-4 carbon atoms, and concrete examples
thereof include ethylidene, propylidene, isopropylidene and isobutylidene.
The cycloolefin type resins (a-1) to (a-4) have an intrinsic viscosity
[.eta.] of from 0.3 to 2.0 dl/g, preferably from 0.4 to 1.2 dl/g as
measured at 135.degree. C. in decalin, a softening temperature (TMA) of
from 70.degree. to 250.degree. C., preferably from 100.degree. to
200.degree. C. as measured by a thermal mechanical analyzer, a glass
transition temperature (Tg) of from 50.degree. to 230.degree. C.,
preferably from 80.degree. to 180.degree. C. and a crystallinity index of
from 0 to 20%, preferably 0 to 2% as measured by X-ray diffractiometry.
In the aforementioned cycloolefin type resins, cycloolefin ring-opening
polymer (a-2) or cycloolefin ring-opening copolymer (a-3) is prepared by
polymerization or copolymerization of cycloolefin or cycloolefins in the
presence of a catalyst comprising halides, nitrate or acetylacetonate of
ruthenium, rhodium, palladium, osmium, indium or platinum, and reducing
agent, or presence of a catalyst comprising halides or acetylacetonate of
titanium, palladium, zirconium or molybdenum, and organoaluminum compound.
The hydrogenated of the ring-opening (co)polymer is prepared by reducing
the cycloolefin random polymer (a-2) or cycloolefin random copolymer (a-3)
obtained above, using hydrogen in the presence of hydrogenating catalyst.
The cycloolefin random copolymer (a-1) is obtained by copolymerization of
ethylene and unsaturated monomer represented by aforementioned formula [I]
in the presence of a catalyst.
The cycloolefins represented by the above-mentioned formula [I] may easily
be prepared by condensing cyclopentadienes with corresponding olefins or
cycloolefins through Diels-Alder reaction.
The cycloolefins represented by the above-mentioned formula [I] used in the
present invention include concretely:
bicyclo[2.2.1]hept-2-ene derivative,
tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10 ]-3-dodecene derivative,
hexacyclo[6.6.1.1.sup.3,6.1.sup.10,13.0.sup.2,7.0.sup.9,14 ]-4-heptadecene
derivative,
octacyclo[8.8.0.1.sup.2,9.1.sup.4,7.1.sup.11,18.1.sup.13,16.0.sup.3,8.0.sup
.12,17 ]-5-docosene derivative,
pentacyclo[6.6.1.1.sup.3,6.0.sup.2,7.0.sup.9.14 ]-4-hexadecene derivative,
heptacyclo-5-eicosene derivative,
heptacyclo-5-heneicosene derivative,
tricyclo[4.3.0.1.sup.2,5 ]-3-decene derivative,
tricyclo[4.3.0.1.sup.2,5 ]-3-undecene derivative,
pentacyclo[6.5.1.1.sup.3,6.0.sup.2,7.0.sup.9,13 ]-4-pentadecene derivative,
pentacyclopentadecadiene derivative,
pentacyclo[4.7.0.1.sup.2,5.0.sup.8,13.1.sup.9,12 ]-3-pentadecene
derivative,
heptacyclo[7.8.0.1.sup.3,6.0.sup.2,7.1.sup.10,17.0.sup.11,16.1.sup.12,15
]-4-eicosene derivative, and
nonacyclo[9.10.1.1.sup.4,7.0.sup.3,8.0.sup.2,10.0.sup.12,21.1.sup.13,20.0.s
up.14,19.1.sup.15,18 ]- 5-pentacosene derivative,
pentacyclo[8.4.0.1.sup.2,5.1..sup.9,12.0.sup.8,13 ]-3-hexadecene
derivative,
heptacyclo[8.8.0.1.sup.4,7.1.sup.11,18.1.sup.13,16.0.sup.3,8.0.sup.12,17
]-5-heneicosene derivative,
nonacyclo[10.10.1.1.sup.5,8.1.sup.14,21.1.sup.16.19.0.sup.2,11.0.sup.2,11.0
.sup.4,9.0.sup.13,22.0.sup.15.20 ]-5-hexacosene derivative,
Concrete examples of the above-mentioned compounds are shown below.
Bicyclo[2.2.1]hept-2-ene derivative including such as those mentioned
below.
##STR4##
Tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10 ]-3-dodecene derivatives such as
those mentioned below.
##STR5##
Hexacyclo[6.6.1.1.sup.3,6.1.sup.10,13.0.sup.2,7.0.sup.9,14 ]-4-heptadecene
derivatives such as those mentioned below.
##STR6##
Octacyclo[8.8.0.1.sup.2,9.1.sup.4,7.1.sup.11,18.1.sup.13,16.0.sup.3,8.0.sup
.12,17 ]-5-docosene derivatives such as those mentioned below.
##STR7##
Pentacyclo[6,6,1,1.sup.3.6,0.sup.2.7,0.sup.9.14 ]-4-hexadecene derivatives
such as those mentioned below.
##STR8##
Heptacyclo-5-eicosene derivatives or heptacyclo-5-heneicosene derivatives
such as those mentioned below.
##STR9##
Tricyclo[4,3,0,1.sup.2.5 ]-3-decene derivatives such as those mentioned
below.
##STR10##
Tricyclo[4.4.0.1.sup.2,5 ]-3-undecene derivatives such as those mentioned
below.
##STR11##
Pentacyclo[6.5.1.1.sup.3,6.0.sup.2,7.0.sup.9.13 ]-4-pentadecene derivatives
such as those mentioned below.
##STR12##
Diene compounds such as mentioned below.
##STR13##
Pentacyclo[4.7.0.1.sup.2,5.0.sup.8,13.1.sup.9.12 ]-3-pentadecene
derivatives such as those mentioned below.
##STR14##
Heptacyclo[7,8,0,1.sup.3.6,0.sup.2.7,1.sup.10.17,0.sup.11.16,1.sup.12.15
]-4-eicosene derivatives such as those mentioned below.
##STR15##
Nonacyclo[9.10.1.1.sup.4,7.0.sup.3,8.0.sup.2,10,0.sup.12,21.1.sup.13,20.0.s
up.14,19.1.sup.15,18 ]-5-pentacosene derivatives such as those mentioned
below.
##STR16##
Pentacyclo[8.4.0.1.sup.2,5.1.sup.9,12.0.sup.8,13 ]-3-hexadecene derivatives
such as those mentioned below.
##STR17##
Heptacyclo[8.8.0.1.sup.4,7.1.sup.11,18.1.sup.13,16.0.sup.3,8.0.sup.12,17
]-5-heneicosene derivatives such as those mentioned below.
##STR18##
Nonacyclo
[10.10.1.1.sup.5,8.1.sup.14,21.1.sup.16,19.0.sup.2,11.0.sup.4,9.0.sup.13,2
2 .0.sup.15,20 ]-6-hexacosene derivatives such as those mentioned below.
##STR19##
In the invention, monomers which are copolymerized with the cycloolefin
represented by formula [I] to form the cycloolefin random copolymer is
ethylene. Olefin compounds other than ethylene may also be copolymerized
with the cycloolefin and ethylene to form the cycloolefin random copolymer
used in the present invention. Examples of other olefin compounds
copolymerizable with ethylene and the cycloolefin compound having the
formula [I] include
.alpha.-olefins having from 3 to 20 carbon atoms such as propylene,
1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene,
1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene;
cycloolefins such as cyclopentene, cyclohexene, 3-methylcyclohexene,
cyclooctene and 3a,5,6,7a-tetrahydro-4,7-methano-1H-indene;
non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene,
5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene,
5-ethylidene-2-norbornene and 5-vinyl-2-norbornene; and
norbornene compounds such as norbornene-2, 5-methylnorbornene-2,
5-ethylnorbornene-2, 5-isopropylnorbornene-2, 5-n-butylnorbornene-2,
5-isobutylnorbornene-2, 5,6-dimethylnorbornene-2, 5-chloronorbornene-2,
2-fluoronorbornene-2 and 5,6-dichloronorbornene-2.
The above-mentioned other olefins can be employed singly or in combination.
The reaction of the above-mentioned olefins such as ethylene with the
cycloolefin having the formula [I] is usually carried out in a hydrocarbon
solvent.
Examples of the hydrocarbon solvents employed in the invention include
aliphatic hydrocarbons such as hexane, heptane, octane and kerosene;
alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and
aromatic hydrocarbons such as benzene, toluene and xylene. Moreover, among
the polymerizable unsaturated monomers used in the preparation of the
olefin polymer having an alicyclic structure, there may also be used, as a
reaction solvent, those monomers which are liquid at a reaction
temperature.
The above-mentioned solvents can be employed singly or in combination.
As catalysts used in the copolymerization reaction of the olefins with the
cycloolefins having the formula [I], there can be employed a catalyst
comprising a vanadium compound and an organoaluminum compound which are
both soluble in the above-described hydrocarbon solvent used as a reaction
medium.
As the vanadium compounds which can be used as a catalyst in the invention,
there can be mentioned compounds having the formula
VO(OR).sub.a X.sub.b or
V(OR).sub.c X.sub.d wherein R is a hydrocarbon group, X is halogen, and a,
b, c and d are numbers satisfying 0.ltoreq.a.ltoreq.3,
0.ltoreq.b.ltoreq.3, 2.ltoreq.a+b.ltoreq.3, 0.ltoreq.c.ltoreq.4,
0.ltoreq.d.ltoreq.4, and 3.ltoreq.c+d.ltoreq.4.
Moreover, the vanadium compounds represented by the above formulas may also
be adducts of an electron donor. Concrete examples of the vanadium
compounds include
VOCl.sub.3,
VO(OC.sub.2 H.sub.5)Cl.sub.2,
VO(OC.sub.2 H.sub.5).sub.2 Cl,
VO(O-iso-C.sub.3 H.sub.7)Cl.sub.2,
VO(O-n-C.sub.4 H.sub.9)Cl.sub.2,
VO(OC.sub.2 H.sub.5).sub.3,
VCl.sub.4,
VOCl.sub.2,
VOBr.sub.2,
VO(O-n-C.sub.4 H.sub.9).sub.3, and
VCl.sub.3.2 (OC.sub.8 H.sub.17 OH)
The above-described vanadium compounds can be employed alone or in
combination.
The electron donors forming the adducts together with the vanadium
compounds are, for example,
oxygen-containing electron donors such as alcohols, phenols, ketones,
aldehydes, carboxylic acids, esters of organic and inorganic acids,
ethers, acid amides, acid anhydrides and alkoxysilanes; and
nitrogen-containing electron donors such as ammonia, amines, nitriles and
isocyanates.
Concrete examples of suitable electron donors include
alcohols having from 1 to 18 carbon atoms, such as methanol, ethanol,
propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl
alcohol, benzyl alcohol, phenylethyl alcohol, isopropyl alcohol, cumyl
alcohol and isopropylbenzyl alcohol;
phenolic compounds having from 6 to 20 carbon atoms, which may have a lower
alkyl group, such as phenol, cresol, xylenol, ethylphenol, propylphenol,
nonylphenol, cumylphenol and naphthol;
ketones having from 3 to 15 carbon atoms, such as acetone, methyl ethyl
ketone, methyl isobutyl ketone, acetophenone, benzophenone and
benzoquinone;
aldehydes having from 2 to 15 carbon atoms, such as acetaldehyde,
propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and
naphthoaldehyde;
organic acid esters having from 2 to 30 carbon atoms, such as methyl
formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate,
octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate,
ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl
(meth)acrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl
benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate,
cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluylate,
ethyl toluylate, amyl toluylate, ethyl ethylbenzoate, methyl anisate,
n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl
cyclohexenecarboxylate, diethyl nadate, diisopropyl tetrahydrophthalate,
diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate,
di-2-ethylhexyl phthalate, .gamma.-butyrolactone, .delta.-valerolactone,
coumarin, phthalide and ethylene carbonate;
acid halides having from 2 to 15 carbon atoms, such as acetyl chloride,
benzoyl chloride, toluyl chloride and anisic acid chloride;
ethers having from 2 to 20 carbon atoms, such as methyl ether, ethyl ether,
isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and
diphenyl ether;
acid amides such as acetamide, benzamide and toluamide;
amines such as methylamine, ethylamine, diethylamine, tributylamine,
piperidine, tribenzylamine, aniline, pyridine, picoline and
tetramethylenediamine;
nitriles such as acetonitrile, benzonitrile and tolunitrile; and
alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane. The
illustrated electron donors may be used alone or in combination.
The organoaluminum compounds used as the catalyst in the invention are
compounds having at least one Al-C bond in the molecule.
One example of such organoaluminum compounds is represented by the formula
(i):
R.sup.1.sub.m Al(OR.sup.2).sub.n H.sub.p X.sub.q (i)
wherein R.sup.1 and R.sup.2 each independently represent a hydrocarbon
group having normally from 1 to 15, preferably from 1 to 4 carbon atoms; X
is halogen; and m, n, p and q are numbers satisfying 0.ltoreq.m.ltoreq.3,
0.ltoreq.n<3, 0.ltoreq.p<3, 0.ltoreq.q<3, and m+n+p+q=3.
Another example of such compounds is a complex alkyl compound of aluminum
and a metal of Group I, represented by the formula (ii):
M.sup.1 AlR.sup.1.sub.4 (ii)
wherein M.sup.1 is Li, Na or K; and R.sup.1 is as defined above.
Examples of the organoaluminum compounds having the formula (i) include:
compounds having the formula of R.sup.1.sub.m Al(OR.sup.2).sub.3-m wherein
R.sup.1 and R.sup.2 are as defined above, and m is a number preferably
satisfying 1.5.ltoreq.m<3;
compounds having the formula of R.sup.1.sub.m AlX.sub.3-m wherein R.sup.1
and X are as defined above, and m is a number preferably satisfying 0<m<3;
compounds having the formula of R.sup.1.sub.m AlH.sub.3-m wherein R.sup.1
is as defined above, and m is a number preferably satisfying 2
.ltoreq.m<3; and
compounds having the formula of R.sup.1.sub.m Al(OR.sup.2).sub.n X.sub.q
wherein R.sup.1, R.sup.2 and X are as defined above, and m, n and q are
numbers satisfying 0<m.ltoreq.3, 0.ltoreq.n<3, 0.ltoreq.q<3 and m +n+q=3.
Concrete examples of the organoaluminum compounds having the formula (i)
include
trialkylaluminum compounds such as triethylaluminum, tributylaluminum and
triisopropylaluminum;
dialkylaluminum alkoxides such as diethylaluminum ethoxide and
dibutylaluminum butoxide;
alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and
butylaluminum sesquibutoxide;
partially alkoxylated alkyl aluminum compounds such as those having an
average composition represented by, for example, the formula of
R.sup.1.sub.2.5 Al(OR.sup.2).sub.0.5 ;
dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum
chloride and diethylaluminum bromide;
alkylaluminum sesquihalides such as ethylaluminum sesquichloride,
butylaluminum sesquichloride and ethylaluminum sesquibromide;
partially halogenated alkylaluminum compounds such as ethylaluminum
dichloride, propylaluminum dichloride and butylaluminum dibromide;
dialkylaluminum hydrides such as diethylaluminum hydride and
dibutylaluminum hydride;
partially hydrogenated alkylaluminum compounds such as ethylaluminum
dihydride and propylaluminum dihydride (alkylaluminum dihydride); and
partially alkoxylated and halogenated alkylaluminum compounds such as
ethylaluminum ethoxychloride, butylaluminum butoxychloride and
ethylaluminum ethoxybromide.
Furthermore, the organoaluminum compounds may be such compounds being
similar to those having the above-mentioned formula (i) as organoalumiunm
compounds in which two aluminum atoms are bonded together via, for
example, an oxygen atom or a nitrogen atom. Concrete examples of such
compounds are as follows:
(C.sub.2 H.sub.5).sub.2 AlOAl(C.sub.2 H.sub.5).sub.2,
(C.sub.4 H.sub.9).sub.2 AlOAl(C.sub.4 H.sub.9).sub.2, and
##STR20##
Examples of the organoaluminum compounds having the formula (ii) include
LiAl(C.sub.2 H.sub.5).sub.4, and
LiAl(C.sub.7 H.sub.15).sub.4.
Among the above-exemplified compounds, particularly preferred are
dialkylaluminum halides, alkylaluminum dihalides and mixtures thereof.
The vanadium compounds are used in such a manner that the concentration of
the vanadium compounds in the reaction system is normally 0.01-5 gram
atom/liter, preferably 0.05-3 gram atom/liter in terms of vanadium atoms.
The organoaluminum compounds are used in such a manner that the ratio of
aluminum atoms to vanadium atoms (Al/V) in the polymerization system is
normally at least 2, preferably 2-50, and particularly preferably 3-20.
The cycloolefin random copolymer (a-1) obtained by using the
above-mentioned catalysts generally contains repeating units derived from
ethylene in an amount of 52 to 90 mol %, preferably 55 to 80 mol %, and
repeating units derived from a cycloolefin in an amount of 10-48 mol %,
preferably 20 to 45 mol %. When the cycloolefin random copolymer comprises
repeating unit derived from .alpha.-olefin other than ethylene, the
cycloolefin random copolymer may generally contain repeating unit derived
from the .alpha.-olefin in an amount of less than 20 mol %, preferably
less than 10 mol %. In the cycloolefin random copolymer, the repeating
units derived from an olefin such as ethylene and the repeating units
derived from a cycloolefin are substantially linearly arranged in the
molecule.
In the cycloolefin copolymer (a-1) used in the invention, it is considered
that the structural units derived from the cycloolefin of the formula [I]
form the repeating units represented by the following formula [II].
##STR21##
wherein m, n, q, R.sup.1 -R.sup.18, R.sup.a and R.sup.b are as defined in
the aforementioned formula [I].
As mentioned previously, it is also possible in the invention to use a ring
opening cycloolefin polymer (a-2) or a ring opening copolymer (a-3)
obtained by ring opening of the same or different cycloolefin monomer or a
hydrogenation product thereof (a-4) in addition to the above-mentioned
cycloolefin random copolymer (a-1). It is considered in this connection
that the above-mentioned ring opening cycloolefin polymer (a-2), ring
opening copolymer (a-3) and hydrogenation production (a-4) thereof are
formed from the cycloolefin represented by the aforementioned formula [I]
which undergoes reaction in the manner as schematized below.
##STR22##
The graft modified cycloolefin resin (b) used in the invention may be
prepared by graft modifying the above-mentioned cycloolefin resin (a-1),
(a-2), (a-3) or (a-4) with an unsaturated carboxylic acid or a derivative
thereof. Examples of the unsaturated carboxylic acid used herein include
acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic
acid, citraconic acid, crotonic acid, isocrotonic acid and nadic acid.TM.
(endocisbicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid). The derivatives
of the above-mentioned unsaturated carboxylic acids are unsaturated
carboxylic acid anhydrides, unsaturated carboxylic acid halides,
unsaturated carboxylic acid amides, unsaturated carboxylic acid imides and
ester compounds of unsaturated carboxylic acids. Concrete examples of
these derivatives include maleyl chloride, maleimide, maleic anhydride,
citraconic anhydride, monomethyl maleate, dimethyl maleate and glycidyl
maleate.
These graft monomers exemplified above may be used either singly or in
combination.
Of the above-exemplified graft monomers, preferred are unsaturated
dicarboxylic acids or derivatives thereof, and particularly preferred are
maleic acid and nadic acid.TM. or acid anhydrides thereof.
The graft modified cycloolefin resin (b) used in the invention may be
prepared, for example, by graft polymerizing the above-mentioned graft
monomer on a cycloolefin resin according to various processes known, per
se. For instance, there is a process wherein the above-mentioned
cycloolefin resin is melted, and the graft monomer is graft polymerized on
the molten cycloolefin resin, or a process wherein the cycloolefin resin
is dissolved in a solvent, and the graft monomer is graft polymerized on
the cycloolefin resin dissolved in the solution. Further, the graft
modified cycloolefin resin may be prepared by a process which comprises
modifying an unmodified-cycloolefin resin by the addition thereto of the
graft monomer so that the resulting modified cycloolefin resin has a
desired graft ratio, or a process which comprises preparing in advance a
graft modified cycloolefin resin having a high graft ratio, and diluting
this cycloolefin resin with an unmodified-cycloolefin resin so that the
diluted cycloolefin resin has a desired graft ratio. In the present
invention, a graft modified cycloolefin resin prepared by any of the
above-mentioned processes may be used. The modification ratio (graft
ratio) of the graft modified cycloolefin resin used in the invention is
usually 0.1-5% by weight, preferably 0.1-4.0% by weight.
In order to make graft copolymerization of the above-mentioned graft
monomer proceed efficiently, the reaction therefor is desirably carried
out in the presence of a radical initiator. The graft reaction is carried
out at a temperature of usually 60.degree.-350.degree. C. The proportion
of the radical initiator used is usually 0.001-5 parts by weight based on
100 parts by weight of the unmodified-cycloolefin resin.
Preferably useful radical initiators include organic peroxides, organic
peresters and azo compounds.
Concrete examples of the useful radical initiators include benzoyl
peroxide, dicumyl peroxide, di-tert-butyl peroxide,
2,5-dimethyl-2,5-di(tert-butylperoxy)hexine-3,
2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and
1,4-bis(tert-butylperoxyisopropyl)benzene.
The cycloolefin resin (a) and the graft modified cycloolefin resin (b) as
illustrated above are used in such an amount that the total amount of the
components (a) and (b) will amount to usually not more than 60 parts by
weight, preferably 10-60 parts by weight based on 100 parts by weight of
the sum total of the components (a), (b), (c) and (d).
Further, the cycloolefin resin (a) which is at least one kind selected from
among (a-1) to (a-4) is used in such an amount that the selected
cycloolefin resin will amount to usually 0-59.5 parts by weight,
preferably 15-55 parts by weight based on 100 parts by weight of the sum
total of the components (a), (b), (c) and (d). The graft modified
cycloolefin resin (b) is used in such an amount that the component (b)
will amount to usually 0.5-60 parts by weight, preferably 5-55 parts by
weight based on 100 parts by weight of the sum total of the components
(a), (b), (c) and (d). Further, the compounding ratio of (a-1) to (a-4)
and (b) is preferably in such a range that the proportion of the sum total
weight of (a-1) to (a-4) used to the weight of (b) used is from 0:60 to
59.5:0.5.
The graft modified elastomer (c) used in the invention is a modified
copolymer having a tensile modulus, as measured according to ASTM D 638 at
23.degree. C., of usually 0.1-2000 kg/cm.sup.2, preferably 1-1500
kg/cm.sup.2.
This graft modified elastomer (c) has a glass transition temperature (Tg)
of usually from -150 to +50.degree. C., preferably from -80.degree. to
-20.degree. C., an intrinsic viscosity [.eta.], as measured in decalin at
135.degree. C., of 0.2-10 dl/g, preferably 1-5 dl/g, a density of usually
0.82-0.96 g/cm.sup.3, preferably 0.84-0.92 g/cm.sup.3, and a
crystallinity index, as measured by x-ray diffractometry, of usually not
more than 30%, preferably not more than 25%.
When kneaded together with the above-mentioned cycloolefin resin (a) and
the graft modified cycloolefin resin (b), the graft modified elastomer (c)
will come to have such a property that at least a part of said elastomer
is finely dispersed in the resulting cycloolefin random copolymer.
When the graft modified elastomer (c) used in the invention is a graft
modified .alpha.-olefin copolymer, such .alpha.-olefin copolymer includes
concretely (c-1) graft modified ethylene/.alpha.-olefin copolymer rubber
and (c-2) graft modified propylene/.alpha.-olefin copolymer rubber. These
copolymer rubber (c-1) and (c-2) may be used either singly or in
combination.
The constituent .alpha.-olefins used in the preparation of the
above-mentioned graft modified ethylene/.alpha.-olefin copolymer rubber
(c-1) may include usually those having 3-20 carbon atoms, for example,
propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene,
1-decene and mixtures thereof. Of these .alpha.-olefins exemplified above,
particularly preferred are propylene and/or 1-butene.
The constituent .alpha.-olefins used in the preparation of the
above-mentioned graft modified propylene/.alpha.-olefin copolymer rubber
(c-2) may include usually those having 4-20 carbon atoms, for example,
1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and
mixtures thereof. Of these .alpha.-olefins exemplified above, particularly
preferred is 1-butene.
So long as no characteristics of .alpha.-olefin copolymer are marred, the
.alpha.-olefin copolymers used in the invention may contain such component
units other than the component units derived from .alpha.-olefins such as
derived from diene compounds.
For example, the above-mentioned other component units permitted to be
contained in the .alpha.-olefin copolymers used in the invention include
component units derived from chain non-conjugated dienes such as
1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene,
6-methyl-1,5-heptadiene and 7-methyl-1,6-octadiene; cyclic non-conjugated
dienes such as cyclohexadiene, dicyclopentadiene, methyltetrahydroindene,
5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene,
5-isopropylidene-2-norbornene and
6-chloromethyl-5-isopropenyl-2-norbornene; and diene compounds such as
2,3-diisopropylidene-5-norbornene,
2-ethylidene-3-isopropylidene-5-norbornene and
2-propenyl-2,2-norbornadiene. The content in the .alpha.-olefin copolymer
of repeating units derived from the above-mentioned diene components is
usually not more than 10 mol %, preferably not more than 5 mol %.
In the graft modified ethylene/.alpha.-olefin copolymer (c-1) used in the
invention, the molar ratio (ethylene/.alpha.-olefin) of ethylene to
.alpha.-olefin, though it varies depending upon the kind of .alpha.-olefin
used, is generally from 10/90 to 90/10, preferably from 50/50 to 90/10.
The above-mentioned molar ratio is preferably from 50/50 to 90/10 when
.alpha.-olefin is propylene, and is preferably from 50/50 to 90/10 when
.alpha.-olefin is that which has not less than 4 carbon atoms.
In the graft modified propylene/.alpha.-olefin copolymer (c-2) used in the
invention, the molar ratio (propylene/.alpha.-olefin) of propylene to
.alpha.-olefin, though it varies depending upon the kind of .alpha.-olefin
used, is generally from 50/50 to 90/10. The above-mentioned molar ratio is
preferably from 50/50 to 90/10 when .alpha.-olefin is 1-butene, and is
preferably from 50/50 to 90/10 when .alpha.-olefin is that which has not
less than 5 carbon atoms.
Of the graft modified .alpha.-olefin copolymers used in the invention,
preferred are graft modified copolymers having the ethylene content of
35-50 mol % and a crystallinity index of not more than 10% obtained by
graft modifying ethylene/propylene random copolymer or
ethylene/.alpha.-olefin random copolymers with graft monomers, because
they are excellent in mechanical properties such as impact strength, etc.
which have been improved by the effect of the invention.
Graft monomers used for preparing the graft modified elastomer (c) in the
invention are preferably unsaturated carboxylic acids or derivatives
thereof. Examples of the unsaturated carboxylic acids include acrylic
acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid,
citraconic acid, crotonic acid isocrotonic acid and nadic.TM. acid
(endocis-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid). The derivatives
of the above-mentioned unsaturated carboxylic acids are unsaturated
carboxylic acid anhydrides, unsaturated carboxylic acid halides,
unsaturated carboxylic acid amides, unsaturated carboxylic acid imides and
ester compounds of unsaturated carboxylic acids. Examples of these
derivatives are concretely malenyl chloride, maleimide, maleic anhydride,
monomethyl maleate, dimethyl maleate and glycidyl maleate.
These graft monomers exemplified above may be used either singly or in
combination.
Of the above-exemplified graft monomers, preferred are unsaturated
dicarboxylic acids or derivatives thereof, particularly maleic acid, nadic
acid.TM. or acid anhydrides thereof.
The graft modified .alpha.-olefin copolymers used in the invention may be
prepared, for example, by modifying .alpha.-olefin copolymers with the
above-mentioned graft monomers according to various processes known, per
se. For example, there is a process wherein the above-mentioned
.alpha.-olefin copolymer is melted, and the graft monomer is graft
polymerized on the molten .alpha.-olefin copolymer, or a process wherein
the .alpha.-olefin copolymer is dissolved in a solvent, and the graft
monomer is graft copolymerized on the .alpha.-olefin copolymer dissolved
in the solution. Further, the graft modified .alpha.-olefin copolymer may
be prepared by a process which comprises modifying an unmodified
.alpha.-olefin copolymer by the addition thereto of the graft monomer so
that the resulting modified .alpha.-olefin copolymer has a desired graft
ratio, or a process which comprises preparing in advance a graft modified
.alpha.-olefin copolymer having a high graft ratio, and diluting this
graft modified .alpha.-olefin copolymer with an unmodified .alpha.-olefin
copolymer so that the diluted graft modified .alpha.-olefin copolymer has
a desired graft ratio. In the invention a graft modified .alpha.-olefin
copolymer prepared by any of the above-mentioned processes may be used.
The modification ratio (graft ratio) of the graft modified .alpha.-olefin
copolymer used in the invention is usually 0.01-5% by weight, preferably
0.1-4% by weight.
In order to make graft copolymerization of the above-mentioned graft
monomer proceed efficiently, it is desirable to carry out the reaction
therefor in the presence of a radical initiator. The graft reaction is
carried out at a temperature of usually 60.degree.-350.degree. C. The
proportion of the radical initiator used is usually 0.001-5 parts by
weight based on 100 parts by weight of the unmodified .alpha.-olefin
copolymer.
Preferably useful radical initiators include organic peroxides and organic
peresters. Concrete examples of such radical initiators include benzoyl
peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl
peroxide, 2,5-dimethyl-2,5-di(peroxybenzoate)hexine-3,
1,4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butyl
peracetate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexine-3,
2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl perbenzoate,
tert-butyl perphenylacetate, tert-butyl perisobutylate, tert-butyl
per-sec-octylate, tert-butyl perpivalate, cumyl perpivalate and tert-butyl
perdiethylacetate. Further, azo compounds may also be used as the radical
initiator in the invention. Concrete examples of the azo compounds include
azobisisobutyronitrile and dimethyl azoisobutylate.
Of the peroxides exemplified above as the radical initiators, preferred are
dialkyl peroxides such as benzoyl peroxide, dicumyl peroxide,
di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexine-3,
2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and
1,4-bis(tert-butylperoxyisopropyl)benzene.
As the graft modified .alpha.-olefin copolymer in the invention, there are
used usually the above-mentioned graft modified ethylene/.alpha.-olefin
copolymer (c-1) and graft modified propylene/.alpha.-olefin copolymer
(c-2), either singly or in combination. However, these copolymers (c-1)
and (c-2) may contain polymers, copolymers or graft modified copolymer
other than the above-mentioned graft modified elastomeric copolymers so
long as no characteristics of the graft modified elastomeric
.alpha.-olefin copolymers are marred.
Other polymers or copolymers as referred to above may be aromatic vinyl
hydrocarbon/conjugated diene copolymers or hydrogenation products thereof.
Concretely, such aromatic vinyl hydrocarbon/conjugated diene copolymers or
hydrogenation products as mentioned above include styrene/butadiene
copolymer rubber, styrene/butadiene/styrene copolymer rubber,
styrene/isoprene block copolymer rubber, styrene/isoprene/styrene block
copolymer rubber, hydrogenated styrene/butadiene/styrene block copolymer
rubber and hydrogenated styrene/isoprene/styrene block copolymer rubber.
The graft modified elastomer (c) as illustrated above is used in the
polyolefin resin composition of the invention containing the components
(a), (b), (c) and (d) in such an amount that the component (c) will amount
to 2-30 parts by weight based on 100 parts by weight of the sum total of
the components (a), (b), (c) and (d). In particular, the amount of the
component (c) used is preferably 5-20 parts by weight.
The polyolefin resin composition containing the component (c) in the amount
as defined above can exhibit improved mechanical characteristics such as
impact strength, etc. without sacrificing excellent characteristics of the
cycloolefin random copolymer (a) contained in said composition.
The polyamide (d) used in the invention are various polyamides obtained,
for example, by polycondensation reaction of diamine component with
dicarboxylic acid component or by ring opening polymerization of a
compound capable of forming amino and carboxyl groups or a functional
derivative thereof.
Concrete examples of the polyamide used in the invention include nylon-6,
nylon-66, nylon-610, nylon-11, nylon-612, nylon-12, copolymerized nylon
formed from caprolactam and aqueous salt solution of nylon, nylon MXD6
formed from methaxylenediamine and adipic acid, nylon-46,
methoxymethylated polyamide, polyhexamethylenediamine terephthalamide and
polyhexamethylenediamine isophthalamide.
The polyamides exemplified above may be used in the invention either singly
or in combination.
The polyamides referred to in the invention are condensates of diamine
component and dicarboxylic acid component or a ring opening polymers of
lactams as mentioned above, and preferred are those having an intrinsic
viscosity [.eta.], as measured in 96% sulfuric acid at 25.degree. C., of
from 0.2 to 2.5 dl/g. In particular, it is preferable to use in the
invention a polyamide having an intrinsic viscosity [.eta.], as measured
in 96% sulfuric acid at 25.degree. C., of from 0.5 to 1.8 dl/g.
The polyamide (d) as illustrated above is used in the polyolefin resin
composition containing the components (a), (b), (c) and (d) of the
invention in such an amount that the component (d) will amount to 20-60
parts by weight based on 100 parts by weight of the total sum of the
components (a), (b), (c) and (d). In the polyolefin resin composition, the
so-called "sea and island structure" can be formed by the component (d)
contained therein in an amount of 20-60 parts by weight. In this case, it
is considered that the resin composition comes to have morphologically the
so-called "sea moiety" formed by the polyamide and the so-called "island
moiety" formed by the components (a), (b) and (c).
In the process for the preparation of the resin composition of the
invention, the above-mentioned components (a), (b), (c) and (d) are mixed
in a molten state and kneaded together. The components (a), (b), (c) and
(d) may be mixed and kneaded together, for example, by a method wherein
these components are mechanically mixed together in the proportion as
defined above, and the resulting mixture in a molten state is kneaded by
means of a melt kneading equipment, for example, a double-screw kneader
(hereinafter this method is sometimes called "batch feed method", or by a
method wherein the components (a), (b) and (c) are mechanically mixed
together in the proportion as defined above, the resulting mixture is
heated to a molten state by means of a melt kneading equipment, for
example, a double-screw kneader, and the component (d) is then added to
the molten mixture, followed by kneading (hereinafter this method is
sometimes called "side feed method"). The polyolefin resin composition of
the invention may be prepared under suitably predetermined conditions by
employing either the above-mentioned batch feed method or side feed
method. In the polyolefin resin composition prepared by the side feed
method as mentioned above, however, the resin particles of the "island
moiety" dispersed in said composition tend to become smaller in particle
diameter and the particle size distribution of said "island moiety" tends
to become narrower, as compared with the polyolefin resin composition
prepared by the batch feed method. This side feed method is illustrated
below in detail.
In the preparation of the polyolefin resin composition according to the
side feed method, the components (a), (b) and (c) are melt kneaded
together in a single or double-screw extruder or a mixer, and the
polyamide (d) is supplied to the molten resin stream, followed by
kneading.
This polyamide (d) may be added in a solid state to the molten resin stream
of the components (a), (b) and (c), or may be supplied in a molten state
to join the molten resin stream of the components (a), (b) and (c),
followed by kneading. In the present invention, it is particularly
preferable that the polyamide in a solid state is added to the molten
resin stream of the components (a), (b) and (c), followed by kneading.
It is possible to prepare the polyolefin resin composition capable of
forming molded articles excellent particularly in low temperature
characteristics, oil resistance and surface glossiness by the side feed
method wherein the solid polyamide (d) is supplied to the molten resin
stream of the components (a), (b) and (c), followed by kneading.
Also, by virtue of the side feed method mentioned above, pellets having the
sea and island structure comprising very small island moieties can be
prepared, and an average diameter of the island moieties is usually not
more than 2 .mu.m and, in most cases, not more than 1 .mu.m.
The conditions under which the molten resin stream of the components (a),
(b) and (c) may be predetermined in accordance with those employed for
kneading resins such as polyolefin, etc. The conditions for kneading the
molten resin stream of the components (a), (b) and (c) to which the
polyamide has been added may also be predetermined in accordance with
commonly used kneading conditions except that the heating temperature
employed is regulated so that a rapid temperature drop due to the addition
of the polyamide will not take place.
In addition to the above-mentioned components, the polyolefin resin
composition of the invention may contain various additives such as
inorganic fillers, organic fillers, heat stabilizers, weathering agents,
antistatic agents, antislip agents, anti-blocking agents, anti-fogging
agents, lubricants, pigments, dyes, natural oil, synthetic oil and wax.
These additives may be added to the resin composition at any stage during
the course of preparation of said composition.
In addition to the purposes for which common polyolefins are used, the
polyolefin resin compositions prepared by the process of the invention are
suitably applicable, in particular, to the field of materials, for which
mechanical strength is required, such as fiber-reinforced PP, ABS resin,
modified polyphenylene oxide, etc.
EFFECT OF THE INVENTION
Molded articles formed by using the polyolefin resin compositions of the
present invention are high in impact strength, excellent in surface
properties particularly less in surface peeling, and surface glossiness.
These molded articles are also low in water absorption properties and high
in oil resistance.
According to the process for the preparation of the polyolefin resin
compositions of the invention, because the cycloolefin resin (a), graft
modified cycloolefin resin (b), graft modified elastomer (c) and polyamide
(d) are melt kneaded together, the polyolefin resin compositions obtained
thereby come to have such characteristics as mentioned above.
In the above-mentioned process of the invention, moreover, by side feeding
the polyamide (d) to the molten resin stream of the components (a), (b)
and (c), the resulting polyolefin resin compositions come to be able to
form the sea and island structure in which the components (a), (b) and (c)
have been finely dispersed in the polyamide (d).
Further, the resin compositions obtained by the process of the invention
have such an advantage over polyamide that the articles being molded out
of said compositions may be lowered not only in molding shrinkage but also
in water absorption.
The present invention is illustrated below with reference to examples, but
it should be construed that the invention is in no way limited to those
examples.
Method of evaluation
Characteristics of the cycloolefin random copolymer and graft modified
elastomer (also called graft modified elastomeric copolymer) used in the
invention, and of the polyolefin resin composition of the invention were
determined in the following manner.
Intrinsic viscosity
The measurement was conducted in decalin at 135.degree. C.
Softening temperature (TMA)
Taken as TMA was the temperature at which a flat-ended needle of 1 mm in
diameter penetrated under a load of 50 g to a depth of 100 .mu.m into a
test specimen heated at a rate of 5.degree. C./min.
Content of graft monomer in graft modified elastomeric copolymer
The measurement was conducted by means of .sup.13 C-NMR.
Crystallinity index
The measurement was conducted by means of X-ray diffractometry at
23.degree. C.
Tensile modulus
A press molded test specimen of 2 mm in thickness was tested for in
accordance with ASTM D 638.
IZ impact strength
An injection molded notched specimen of 1/8 inch in thickness was tested
for at 23.degree. C. in accordance with ASTM D 256.
Initial flexural modulus (FM)
An injection-molded specimen of 1/8 inch in thickness was tested for at
23.degree. C. and a crosshead speed of 20 mm/min in accordance with ASTM D
790.
Flexural yield stress (FS)
The same test as in FM was conducted.
Glossiness (Gloss)
An injection-molded square plate of 2 mm in thickness was tested at
23.degree. C. and an angle of incidence of 60.degree. in accordance with
ASTM D 523.
Melt index (MI)
The measurement was conducted at 260.degree. C. under a load of 2.16 kg in
accordance with JIS-K-6760.
Cyclohexane and water absorption
A test specimen, 100 mm.times.100 mm.times.2 mm, was immersed for 72 hours
in cyclohexane or water, the cyclohexane or water remaining on the surface
of the specimen was removed, the thus immersed specimen was then weighed
to obtain an increase in weight, and the increment was represented by
percentage on the weight of the specimen prior to immersion.
Sample Preparation Example 1
Cycloolefin copolymer (a-1)
Copolymerization reaction of ethylene with
tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10 ]dodecene-3 (hereinafter sometimes
abbreviated to "TCD-3") was carried out continuously using a 1-liter
reactor equipped with a stirring blade. That is, there were continuously
fed to the reactor through the upper portion thereof a cyclohexane
solution of TCD-3 at a rate of 0.4 l/hr so that the concentration in the
reactor of TCD-3 becomes 60 g/l, a cyclohexane solution of VO(OC.sub.2
H.sub.5)Cl.sub.2 as a catalyst at a rate of 0.5 l/hr so that the vanadium
concentration in the reactor becomes 0.5 mmol/l (in this case, the
concentration of vanadium to be fed is 2.86 times the vanadium
concentration in the reactor), a cyclohexane solution of ethylaluminum
sesquichloride Al(C.sub.2 H.sub.5).sub.1.5 Cl.sub.1.5 at a rate of 0.4
l/hr so that the aluminum concentration in the reactor becomes 4.0 mmol/l,
and cyclohexane at a rate of 0.7 l/hr. On the one hand, the polymer
solution was withdrawn continuously from the reactor through the lower
portion thereof so that the polymer solution in the reactor always amounts
to 1 liter (that is, the retention time becomes 0.5 hour).
To the polymerization system were fed ethylene at a rate of 20 l/hr,
nitrogen at a rate of 10 l/hr and hydrogen at a rate of 0.5 l/hr using a
bubbling tube.
The copolymerization reaction was carried out at a temperature kept at
10.degree. C. by means of circulation of a cooling medium in a jacket
surrounding the reactor.
The copolymerization reaction carried out under the polymerization
conditions mentioned above resulted in the preparation of an
ethylene/TCD-3 random copolymer.
That is, the polymerization reaction was stopped by adding a
cyclohexane/isopropyl alcohol mixture (1/1 volume ratio) to the polymer
solution withdrawn from the reactor through the lower portion thereof.
Thereafter, 1 liter of an aqueous solution containing 5 ml of concentrated
hydrochloric acid and the polymer solution withdrawn are brought into
contact with each other in the proportion of 1:1, while strongly stirring
them by means of a homomixer, whereby the residual catalyst was allowed to
migrate to an aqueous phase.
The mixture thus resulted was allowed to stand, the aqueous phase was
removed therefrom, the polymer solution was purified by washing twice with
distilled water and then isolated.
The polymer solution thus isolated was brought into contact with acetone
amounting to three times as much as the polymer solution while stirring
them strongly, and the solids thereby precipitated were collected by
filtration, followed by thorough washing with acetone. The solids thus
collected were then dried for 24 hours in a stream of nitrogen at
130.degree. C. and 350 mmHg.
By carrying out continuously a series of operations mentioned above, an
ethylene/TCD-3 random copolymer was prepared at a rate of 76 g/hr (36
g/l).
From the results obtained in .sup.13 C-NMR analysis of this copolymer, it
was found that the ethylene content in the copolymer is 63 mol %.
Furthermore this copolymer had an intrinsic viscosity [.eta.], as measured
in decalin at 135.degree. C., of 0.5 dl/g, an iodine value of 1.0 and TMA
of 150.degree. C.
Hereinafter, this cycloolefin random copolymer (a-1) is referred to as
"PO-1".
Sample Preparation Example 2
Cycloolefin copolymer (a-1)
Sample Preparation Example 1 was repeated except that ethylene was fed at a
rate of 10 l/hr and hydrogen was fed at a rate of 0.3 l/hr, whereby an
ethylene/TCD-3 copolymer was prepared.
From the results obtained in .sup.13 C-NMR analysis of this copolymer, it
was found that the ethylene content in the copolymer is 56 mol %.
Furthermore, this copolymer had an intrinsic viscosity [.eta.], as
measured in decalin at 135.degree. C., of 0.7 dl/g, an iodine value of 1.0
and TMA of 180.degree. C.
Hereinafter, this cycloolefin random copolymer (a-1) is referred to as
"PO-2".
Sample Preparation Example 3
Graft modified cycloolefin copolymer (b)
A mixture of 100 parts by weight of "PO-1" obtained in Sample Preparation
Example 1, 1 part by weight of maleic anhydride and 0.2 part by weight of
2,5-dimethyl-2,5-di(t-butylperoxy) hexine-3 (trade name Perhexine 25B, a
product of Nippon Oils And Fats Co., Ltd.) was melt kneaded at 260.degree.
C. using a double-screw extruder equipped with a vent of 30 mm in diameter
to obtain a graft modified cycloolefin copolymer (b).
The content of grafted maleic anhydride unit in the graft modified
cycloolefin copolymer obtained was 0.83% by weight.
Hereinafter, this graft modified cycloolefin copolymer (b) is referred to
as "GPO-1".
Sample Preparation Example 4
Graft modified cycloolefin copolymer (b)
A mixture of 100 parts by weight of "PO-2" obtained in Sample Preparation
Example 2, 1 part by weight of maleic anhydride and 0.2 part by weight of
2,5-dimethyl-2,5-di(t-butylperoxy) hexine-3 (trade name Peroxine 25B, a
product of Nippon Oils And Fats Co., Ltd.) was melt kneaded at 260.degree.
C. using a double-screw extruder equipped with a vent of 30 mm in diameter
to obtain a graft modified cycloolefin copolymer (b).
The content of the grafted maleic anhydride unit in the graft modified
cycloolefin copolymer obtained was 0.81% by weight.
Hereinafter, this graft modified cycloolefin copolymer (b) is referred to
as "GPO-2".
Sample Preparation Example 5
Graft modified cycloolefin copolymer (b)
A mixture of 100 parts by weight of "PO-2" obtained in Sample Preparation
Example 2, 1 part by weight of maleic anhydride and 0.05 part by weight of
2,5-dimethyl-2,5-di(t-butylperoxy) hexine-3 (trade name Perhexine 25B, a
product of Nippon Oils And Fats Co., Ltd.) was melt kneaded at 260.degree.
C. using a double-screw extruder equipped with a vent of 30 mm in diameter
to obtain a graft modified cycloolefin copolymer (b).
The content of the grafted maleic anhydride unit in the graft modified
cycloolefin copolymer obtained was 0.26% by weight.
Hereinafter, this graft modified copolymer (b) is referred to as "GPO-3".
Sample Preparation Example 6
Graft modified elastomer (c)
A mixture of 100 parts by weight of an ethylene/propylene copolymer having
the ethylene content of 80 mol % and an intrinsic viscosity [.eta.], as
measured in decalin at 135.degree. C., of 2.2 dl/g (this copolymer is
referred to as "MP-0"), 1 part by weight of maleic anhydride and 0.2 part
by weight of 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3 was melt kneaded
at 260.degree. C. using a double-screw extruder equipped with a vent of 30
mm in diameter to obtain a graft modified elastomer (c).
The content of the grafted maleic anhydride unit in the graft modified
elastomer obtained was 0.90% by weight. The graft modified elastomer (c)
has a tensile modulus of 80 kg/cm.sup.2.
Hereinafter, this graft modified elastomer is referred to as "MP-1".
Sample Preparation Example 7
Graft modified elastomer (c)
Sample Preparation Example 6 was repeated except that in place of 1 part by
weight of the maleic anhydride, 1 part by weight of glycidyl methacrylate
was used, whereby a graft modified elastomer (c) was prepared.
The content of the grafted glycidyl methacrylate unit in the graft modified
elastomer obtained was 0.90% by weight. The graft modified elastomer (c)
has a tensile modulus of 80 kg/cm.sup.2.
Hereinafter, this graft modified elastomer (c) is referred to as "MP-2".
EXAMPLE 1
A polyolefin resin composition was prepared by using a double-screw
extruder having a die of 30 mm in diameter, said extruder being designed
as to be capable of feeding a resin or resin composition during melt
kneading operation to the resin or resin composition being melt kneaded in
the extruder.
Hereinafter, the fact that a resin or resin composition (A) is fed in the
above-mentioned extruder to the resin or resin composition (B) being melt
kneaded in said extruder is expressed by saying "A is side fed to B". In
contrast thereto, the fact that A and B are melt kneaded in a batch is
expressed by saying "A and B are fed in a batch".
Using the above-mentioned extruder (preset temperature: 230.degree. C.), 30
parts by weight of the cycloolefin random copolymer (PO-1) obtained in
Sample Preparation Example 1, 10 parts by weight of the elastomer (GPO-1)
obtained in Sample Preparation Example 3 and 10 parts by weight of the
graft modified elastomer (MP-1) obtained in Sample Preparation Example 6
were kneaded together to prepare a resin composition. To 100 parts by
weight of this resin composition, 100 parts by weight (the same amount as
that of the above-mentioned resin composition) of a polyamide resin (nylon
6, a product of Toray Ind. Inc. under a trade name of Amiran CM 1007) was
side fed to prepare a polyolefin resin composition.
The polyolefin resin composition dried for 8 hours at 120.degree. C. was
molded into a test specimen and a square plate for examination of physical
properties using an injection molding machine (30 EPN of Toshiba IS) at a
molding temperature of 270.degree. C. and a mold temperature of 70.degree.
C.
Physical properties of the test specimens as measured are shown in Table 1.
As is clear from the results shown in Table 1, the composition prepared was
excellent in impact strength, rigidity, heat resistance, glossiness and
oil resistance.
Subsequently, the test specimen was dyed with ruthenic acid or osmic acid
to prepare a specimen for transmission electron microscopic observation.
On observation of the specimen under a transmission electron microscope,
it was found that spherical or elliptical dispersed particles having an
average particle diameter of not more than 1 .mu.m are present in the
specimen.
EXAMPLE 2
Example 1 was repeated except that nylon 6,6 (trade name: Amiran CM 3001-N,
a product of Toray Ind. Inc.) was used as the polyamide resin and the
extrusion temperature employed was changed to 260.degree. C., whereby a
polyolefin resin composition was prepared, and a test specimen and a
square plate were prepared therefrom.
Physical properties of the specimens as measured are shown in Table 1.
As is clear from the results shown in Table 1, the composition prepared was
excellent in impact strength, rigidity, heat resistance, glossiness and
oil resistance.
Subsequently, a specimen for transmission electron microscopic observation
was prepared in the same manner as in Example 1. On observation of the
specimen under a transmission electron microscope, it was found that
spherical or elliptical dispersed particles having an average particle
diameter of not more than 1 .mu.m are present in the specimen.
EXAMPLE 3
Example 1 was repeated except that the proportions of the cycloolefin
random copolymer, graft modified cycloolefin random copolymer and graft
modified elastomer used were changed to those as shown in Table 1, whereby
a polyolefin resin composition was prepared, and a test specimen and a
square plate were prepared therefrom.
Physical properties of the specimens obtained are shown in Table 1.
As is clear from the results shown in Table 1, the composition prepared was
excellent in impact strength, rigidity, heat resistance, glossiness and
oil resistance.
Subsequently, a specimen for transmission electron microscopic observation
was prepared in the same manner as in Example 1. On observation of the
specimen under a transmission electron microscope, it was found that
spherical or elliptical dispersed particles having an average particle
diameter of not more than 1 .mu.m are present in the specimen.
EXAMPLE 4-5
Example 1 was repeated except that the proportions of the cycloolefin
random copolymer (PO-1), graft modified cycloolefin random copolymer
(GPO-2) and graft modified elastomer (MP-1) used were changed to those as
shown in Table 1, whereby polyolefin resin compositions were prepared, and
test specimens and square plates were prepared therefrom.
Physical properties of the specimens obtained are shown in Table 1.
As is clear from the results shown in Table 1, the compositions obtained
were excellent in impact strength, rigidity, heat resistance, glossiness
and oil resistance.
Subsequently, specimens for transmission electron microscopic observation
were prepared in the same manner as in Example 1. On observation of the
specimens under a transmission electron microscope, it was found that
spherical or elliptical dispersed particles having an average particle
diameter of not more than 1 .mu.m are present in the specimens.
EXAMPLE 6
Example 4 was repeated except that "MP-2" was used in place of the "MP-1",
whereby a polyolefin resin composition was prepared, and a test specimen
and a square plate were prepared therefrom.
Physical properties of the specimens obtained are shown in Table 1.
As is clear from the results shown in Table 1, the composition prepared was
excellent in impact strength, rigidity, heat resistance, glossiness and
oil resistance.
Subsequently, a specimen for transmission electron microscopic observation
was prepared in the same manner as in Example 1. On observation of the
specimen under a transmission electron microscope, it was found that
spherical or elliptical dispersed particles having an average particle
diameter of not more than 1 .mu.m are present in the specimen.
EXAMPLE 7
Example 1 was repeated except that the proportions of the resins used were
changed to those as shown in Table 1, whereby a polyolefin resin
composition was prepared, and a test specimen and a square plate were
prepared therefrom.
Physical properties of the specimens obtained are shown in Table 1.
The composition thus obtained was excellent in impact strength, rigidity
and heat resistance, though the composition did not show distinguished oil
resistance.
Subsequently, a specimen for transmission electron microscopic observation
was prepared in the same manner as in Example 1. On observation of the
specimen under a transmission electron microscope, it was found that
spherical or elliptical dispersed particles having an average particle
diameter of not more than 1 .mu.m are present in the specimen.
EXAMPLE 8
Example 7 was repeated except that the proportion of the cycloolefin random
copolymer (PO-2) and graft modified elastomer (MP-1) used were changed to
those as shown in Table 1, whereby a polyolefin resin composition was
prepared, and a test specimen and a square plate were prepared therefrom.
Physical properties of the specimens obtained are shown in Table 1.
The composition thus obtained was excellent in impact strength, rigidity
and heat resistance, though the composition did not show distinguished oil
resistance.
Subsequently, a specimen for transmission electron microscopic observation
was prepared in the same manner as in Example 1. On observation of the
specimen under a transmission electron microscope, it was found that
spherical or elliptical dispersed particles having an average particle
diameter of not more than 1 .mu.m are present in the specimen.
EXAMPLE 9
Example 8 was repeated except that the cycloolefin random copolymer (PO-2)
was not used, and the graft modified cycloolefin random copolymer (GPO-3)
n substitution for the GPO-1 and the graft modified elastomer (MP-1) were
used in the amount as shown in Table 1, whereby a polyolefin resin
composition was prepared, and a test specimen and a square plate were
prepared therefrom.
Physical properties of the specimens obtained are shown in Table 1.
The composition thus obtained was excellent in impact strength, rigidity
and heat resistance, though the composition did not show distinguished oil
resistance.
Subsequently, a specimen for transmission electron microscopic observation
was prepared in the same manner as in Example 1. On observation of the
specimen under a transmission electron microscope, it was found that
spherical or elliptical dispersed particles having an average particle
diameter of not more than 1 .mu.m are present in the specimen.
EXAMPLE 10
Example 1 was repeated except that the cycloolefin random copolymer (PO-2)
in substitution for the PO-1 and the graft modified Cycloolefin random
copolymer (GPO-1) were used in the amounts as shown in Table 1 and melt
kneaded together to form a molten resin composition, and pellet prepared
in advance by melt kneading the graft modified elastomer (MP-1) and the
polyamide (CM1007) together were side fed to the molten resin composition,
whereby a polyolefin resin composition was prepared, and a test specimen
and a square plate were prepared therefrom.
Physical properties of the specimens obtained are shown in Table 1.
As evidenced by the thus obtained specimens having the physical properties
as shown in Table 1, the resin composition obtained was excellent in oil
resistance, impact strength, rigidity and heat resistance.
Subsequently a specimen for transmission electron microscopic observation
was prepared in the same manner as in Example 1. On observation of the
specimen under a transmission electron microscope, it was found that
spherical or elliptical dispersed particles having an average particle
diameter of not more than 1 .mu.m are present in the specimen.
EXAMPLE 11
Example 1 was repeated except that the resin components used were changed
to those as shown in Table 1, and the components were melt kneaded
together in a batch, whereby a polyolefin resin composition was prepared.
The test specimens were prepared in the same manner as in Example 1 and
were observed under a transmission electron microscope in the same way as
in Example 1, whereupon the dispersed particles observed had an average
particle diameter of not more than 3 .mu.m.
EXAMPLE 12
Example 3 was repeated except that the resin components used were changed
to those as shown in Table 1, and the components were melt kneaded
together in a batch, whereby a polyolefin resin composition was prepared.
The test specimens were prepared from the polyolefin resin composition in
the same manner as in Example 1.
Physical properties of the specimens obtained are shown in Table 1. The
specimens thus obtained were observed under a transmission electron
microscope in the same manner as in Example 1, whereupon the dispersed
particles observed has an average particle diameter of not more than 3
.mu.m.
COMPARATIVE EXAMPLE 1
Example 6 was repeated except that the ethylene/propylene copolymer MP-0
was used instead of the graft modified elastomer, whereby a polyolefin
resin composition was obtained.
Physical properties of the test specimens obtained from the polyolefin
composition are shown in Table 1. The composition thus obtained was poor
in impact strength, though the composition was excellent in rigidity, heat
resistance and glossiness.
TABLE 1 (1-1)
__________________________________________________________________________
Graft
modified
Cyclo- cyclo-
Graft
olefin olefin
modi-
random random
fied IZ Oil Water
co- co- elasto-
Poly-
Resin (kg.
FM MI resis-
absorp-
polymer polymer
mer amide
composition
Feed
cm/
(kg/
(g/10
Gloss
TMA tance
tion
(a-1) (b) (c) (d) (a-1)/(b)/(c)/(d)
method
cm)
cm.sup.2)
min.)
(%) (.degree.C.)
(%) (%)
__________________________________________________________________________
Ex. 1
PO-1 GPO-1
MP-1
CM1007
30/10/10/50
Side
44 22100
10.4
95 189 +0.2
+0.8
feed
Ex. 2
PO-1 GPO-1
MP-1
CM3001-
30/10/10/50
Side
30 22300
-- 47 223 +0.1
--
N feed
Ex. 3
PO-1 GPO-1
MP-1
CM1007
25/10/15/50
Side
61 19700
10.0
96 188 +1.6
+0.8
feed
Ex. 4
PO-2 GPO-2
MP-1
CM1007
30/10/10/50
Side
30 24400
8.5 91 191 +0.2
+0.8
feed
Ex. 5
PO-2 GPO-2
MP-1
CM1007
20/20/10/50
Side
30 25000
7.0 90 192 +0.2
+0.8
feed
Ex. 6
PO-2 GPO-2
MP-2
CM1007
30/10/10/50
Side
30 24300
9.3 86 191 +0.2
+0.8
feed
Ex. 7
PO-1 GPO-1
MP-1
CM1007
35/10/15/40
Side
46 20600
9.4 93 148 +4.6
--
feed
Ex. 8
PO-2 GPO-1
MP-1
CM1007
35/10/15/40
Side
60 18700
8.1 79 164 +4.3
+0.8
feed
Ex. 9
-- GPO-3
MP-1
CM1007
0/40/10/50
Side
30 23800
13.0
92 195 +0.5
+0.8
feed
Ex. 10
PO-2 GPO-1
MP-1
CM1007
30/10/10/50
Side
24 22000
8.5 89 179 +0.3
+0.8
feed
Ex. 11
PO-1 GPO-1
MP-1
CM1007
20/20/15/45
batch
31 18300
0.1 70 184 -- +0.4
feed
Ex. 12
PO-1 GPO-1
MP-1
CM1007
25/10/15/50
batch
50 19000
11.0
85 178 +4.5
+0.9
feed
Com-
PO-2 GPO-2
Graft
CM1007
30/10/10/50
Side
6 22000
12.2
90 180 +1.8
+0.8
para- unmod- feed
tive ified
Ex. 1 MP-0
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